Process of breaking emulsions



United States Patent 3,344,083 PROCESS OF BREAKING EMULSIONS Woodrow J. Dickson, La Habra, and Fred W. Jenkins, Bnena Park, Califl, assignors to Petrolite Corporation, a corporation of Delaware No Drawing. Division of application Ser. No. 47,387, Aug. 4, 1960. Continuation of application Ser. No. 115,877, June 9, 1961. This application Mar. 4, 1966, Ser. No. 531,793

6 Claims. (Cl. 252344) This application is a division of application Serial No. 47,387, filed on Aug. 4, 1960, and is copending with application Serial No. 458,373, filed on May 24, 1965, now abandoned, as a division of said application Serial No. 458,373, and is also a continuation of application Serial No. 115,877, filed on June 9, 1961, now abandoned and is copending with each of the following applications:

(1) Ser. No. 505,037, Oct. 24, 1965, Fuel Composition; (2) Ser. No. 115,876, June 9, 1961, Process of Preventing Scale, granted as U.S. Patent No. 3,251,778 on May 17, 1966; (3) Ser. No. 505,039, Oct. 24, 1965, Preventing Corrosion, granted as U.S. Patent No. 3,262,791 on July 26, 1966; (4) Ser. No. 115,878, June 9, 1961, Lubricating Composition, now Patent No. 3,301,783; (5) Ser. No. 115,881, June 9, 1961, Inhibiting Foam, now abandoned; (6) Ser. No. 115,882, June 9, 1961, Flotation Process, now abandoned; (7) Ser. No. 115,883, June 9, 1961, Drilling Fluids, now abandoned; (8) Ser. No. 115,- 884, June 9, 1961, Treatment of Oil Wells, now abandoned; (9) Ser. No. 308,063, Sept. 11, 1963, Anti-Stripping Agents, granted as U.S. Patent No. 3,259,513 on July 5, 1966.

This invention relates to polyalkyleneimines and to derivatives thereof. More particularly, this invention relates to polyethyleneimine and to polyethyleneimine derivatives containing various groups, such as the oxyalkylated, acylated, alkylated, carbonylated, olefinated, etc., derivatives thereof, prepared by introducing such groups individually, alternately, in combination, etc., in cluding for example, derivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emulsions; as demulsifiers for oil-in-water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like, as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as anti-oxidants, gasoline stabilizers, fungicides, etc.; as

[flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphalt-mineral aggregate compositions; as additives for compositions useful in acidizing calcareous stratas of oil wells; as additives for treating water used in the secondary recovery of oil and in disposal wells; as additives used in treating oil Well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-inwater and water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing mud sheaths from newly drilled wells; as dehazing or foginhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing Water-vapor impermeable paper board; as agents in paraflin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and anti-stalling agents for gasoline; preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, for example, as mercerizing assistants, as Wetting agents, as rewetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as anti-static agents for rugs, floors, upholstery, plastic and wax polishes, textiles, etc.; as detergents useful in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents useful in leather processes such as in flat liquoring, pickling, acid degreasing, dye fixing, and the like; as agents in metal pickling; as additives in paints for improved adhesion of primers, in preventing water-spotting in lacquer; as anti-skinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink; as agents in the preparation of wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 24-D (Toxaphene), chlordane, nicotine sulfate, hexaehloracyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulating building materials; and the like.

Polyalkyleneimine employed in this invention include high molecular weight polyethyleneirnine, i.e. polymers of ethyleneimine,

as antiseptic,

Ugh/CH2 or substituted products thereof:

CRz-CR': CR2CR'3 etc. H I

wherein R, R and R" are hydrogen or a substituted group, for example a hydrocarbon group such as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, etc., 'but preferably hydrogen or alkyl.

Thus, polyethyleneirnine is polymerized, substituted or an unsubstituted, 1,2-alkyleneimine. Although polyethyleneimine is the preferred embodiment, other illustrative examples include, for example,

CH2 1,2-propyleneimine /CHC2H5 HN\I 0H, 1,2-butyleneimine /OHOH3 a:

OH-OH3 2,3-bu'tyleneimine Cf-bu-tyleth yleneimine OHC12 2s CH2 C-dodecylethyleneimine CH Cl8I' 37 CH3 C-octadecylethyleneimine A preferred class of polymerized 1,2 alkyleneimines include those derived from polymerizing RCH-RCH H wherein R and R are hydrogen or an alkyl radical, the latter being the same or different. Of the substituted ethyleneimines, propyleneimines are preferred.

The polyethyleneimines useful herein have molecular weights of, for example, at least 800, for example from 800 to 100,000 or higher, but preferably 20,000 to 75,000 or higher. There is no upper limit to the molecular weight of the polymer employed herein and molecular weights of 200,000, 500,000 or 1,000,000 or more can be employed.

The optimum molecular weight will depend on the particular derivative, the particular use, etc.

Although these products are generally prepared by polymerizing 1,2 alkyleneimines, they may also be prepared by other known methods, for example, by decarboxylating 2-oxazolidine as described inv 2,806,839, etc.

Commercial examples of these compounds are available, for example, those sold by the Chemirad Corporation as PEI in a 50% by weight aqueous solution having a molecular weight of 30-40,000. Propyleneimine is also commercially available and suitable polymers can be prepared from this material.

For convenience and simplicity, this invention will be illustrated by employing polyethyleneimine.

Polyethyleneimine is a well known polymer whose preparation from ethyleneimine is described in US. Patent 2,182,306 and elsewhere. For convenience in polymerizing and handling, the polymer is generally prepared as an aqueous solution. Water can be removed, if desired, by distilling the water therefrom or by azeotroping the water therefrom in the presence of a hydrocarbon, such as xylene, and using the solution and/ or suspension obtained thereby for further reaction or use. The following polyethyleneimines of the molecular weights indicated are employed herein to illustrate this invention.

Polymer designation:

Polyethyleneimine- Aprox. mol. wgt. range 900 800-1000 5,000 4000-6000 11,500 10,500-12,500 20,000 18,000-22,000 35,000 30,00040,000 50,000 40,000-60,000 75,000 65,00085,000 100,000 80,000-125,000

ACYLATION which are well known to those skilled in the art, are applicable.

Acylation is conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from to 280 C., but preferably at to 200 C.

The product formed on acylation will vary with the particular conditions employed. First the salt, then the amide is formed. If, however, after forming the amide at a temperature between l40-250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid group employed, the first mole of water being evolved during amidification. The product formed in such cases contains a cyclic amidine ring, such as an imidazoline or a tetrahydropyrirnidine ring. Infrared analysis is a convenient method of determining the presence of these groups.

Water is formed as a by-product of the reaction between the acylating agent and polyethyleneimine. In order to facilitate the removal of this water, to effect a more complete reaction in accordance with the principle of LeChatelier, a hydrocarbon solvent which forms an azeotropic mixture with water can be added to the reaction mixture. Heating is continued with the liquid reaction mixture at the preferred reaction temperature, until the removal of water by azeotropi-c distillation has substantially ceased. In general, any hydrocarbon solvent which forms an azeotropic mixture with water can be used. It is preferred, however, to use an aromatic hydrocarbon solvent of the benzene series. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and the reaction temperature selected. Accordingly, a sufficient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction can also be removed by operating under reduced pressure. When operating with a reaction vessel equipped with a reflux condenser provided with a water takeoff trap, sufficient reduced pressure can be achieved by applying a slight vacuum to the upper end of the condenser. The pressure inside the system is usually reduced to between about 50 and about 300 millimeters. If desired, the water can be removed also by distillation, while operating under relatively high temperature conditions.

The time of reaction between the acylating agent and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the water from the reaction mixture. In practice, the reaction is continued until the formation of water has substantially ceased. In general, the time of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products, carboxylic acids having more than six carbon atoms and less than 40 carbon atoms but preferably 8-30 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally-occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and a-ralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, oa-proic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, pahnitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, triconsanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, anglic, teglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, mynstoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoie acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosem'c acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxy-myristic acids, the hydroxypentadecanoic acids, the hydroxy-palmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy ste-aric acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fenchlolic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xyleneic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acid-s are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, a-conitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid is utilizable for the production of the reaction products of the present invention. The general structural formulae of these compounds are:

wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in accordance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. Nevertheless, the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Ac cordingly, when the term alkenyl succinic acid anhydride, is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore. Non-limiting examples of the alkenyl succinic acid anhydride reactant are ethenyl succinic acid anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2-ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiod-ooctyl succinic acid; octenyl succinic acid anhydride; Z-methyl-heptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2- isopropylpentenyl succinic acid anhydride; nonenyl succinic acid anhydride; 2-propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; 5-methyl-2-isopropylhexenyl' succinic acid anhydride; 1,Z-dibromo-2-ethylocteny1 succinic acid anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid; 3- ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinic acid anhydride; dodecenyl succinic acid; 2- propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized octadecenyl succinic acid; octadecyl succinic acid anhydride; 1,2-dibrom-2- methylpentadecenyl succinic acid anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,2-dichloro-2-methylnonadecenyl succinic acid anhydride; 2-0ctyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difficult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable herein.

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cylic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.

wherein P=the polyethyleneimine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecularly with polyethyleneimine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with polyethyleneimine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced, i.e., by acylation.

The moles of acylating agent reacted with polyethyleneimine will depend on the number of acylation reactive positions contained therein as well as the number of moles of acylating agent one wishes to incorporate into the polymer. Theoretically one mole of acylating agent can be reacted per amino group on the polyethyleneimine molecule. We have advantageously reacted 1-20 moles of acylating agent per mole of polyethylene 900, but preferably l-l2 moles. Proportionately greater amounts of acylating agent can be employed with polyethyleneimine of higher molecular weight. Thus, with polyethyleneimine 20,000, 1-50 moles of acylating agent can be employed, and with polyethyleneimine 35,000, 1-100 moles can be employed, etc. Optimum acylation will depend on the particular use.

The following examples are illustrative of the preparation of the acylated polyethyleneimine.

The following general procedure is employed in acylating. A xylene suspension of polyethyleneimine, after the removal of water, is mixed with the desired ratio of acid. Heat is then applied. After the removal of the calculated amount of Water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from to 200 C. Where the formation of the cyclic amidine type structure is desired, the maximumtemperature is generally 180-250 C. and more than one mole of water per carboxylic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example I-A- The reaction is carried out in a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle to 1 mole (900 grams) of polyethyleneimine 900 in an equal weight of xylene (i.e., 900 grams, 200 grams of lauric acid (1 mole) is added with stirring in about ten minutes. The reaction mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 19 grams (1.1 mole) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20 mm. The product is a dark, viscous, xylene soluble liquid.

Example 1-A The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 36 grams (2 moles) of Water are removed instead of 19 grams (1.1 mole). Infrared analysis of the product indicates the presence of a cyclic amidine ring.

The following examples of acylated polyethyleneimines are prepared in the manner of the above examples from the polyethyleneimine noted in the following table. The products obtained are dark, viscous materials.

In the examples the symbol A identifies the acylated polyethyleneimine. Thus, specifically 1-A, represents acylated polyethyleneimine.

TABLE I.ACYLATED rg p pggrs OF POLYETHYLENE Molecular Ratio Weight of Ratio Mols of Ex. Acid Polyethyl- Mols of Water eneimine Acid Per Removed (PE) M01 of PE Per M01 of Acid 1Al- Laurie (200) 900 10:1 1. 12 1A2 do 900 8:1 1.3 900 6:1 1. 5 900 5:1 1.1 900 4:1 1. 85 900 1:1 2.0 900 1:1 1. 1 5,000 6:1 1. 3 5, 000 5:1 1. 02 5, 000 4:1 1. 6 5, 000 1:1 2.0 1 11, 500 10:1 1. 3 d 11,500 5:1 1. 8 3-A; do 11,- 0 2:1 1.1

TABLE I.-Continued Molecular Ratio Weight of Ratio Mols of Ex. Acid Polycthyl- Mols of Water eneimine Acid Per Removed (PE) M01 of PE Per M01 of Acid 3A4 Acetic (60) 11, 500 1:1 1. 2 -Ar--- Palmitic (256.4) 11. 500 3:1 1. 6 4-A2 .do 11,500 2:1 1.3 4-113 (10.. 11, 500 1:1 2. 5-A1 Stearic (284) 20, 000 3:1 1. 4 5-Az d0 20, 000 2:1 1. 1 6A1 Dimeric (600) (Emery 20, 000 3:1 1. 5

Industries) 50, 000 4:1 1. 6 9A3- ..dn 50, 000 221 1. 4 l0-A Naphthcnic (330) 50, 000 2:1 1. 8

(Sunaptic Acid B). 10A1 do 50,000 1:1 1.2 11-A1 Maleic Anhydride (98).. 50, 000 1:1 11Az 50, 000 0.8:1 50, 000 1:2 100, 000 2:1 100, 000 1:1 100, 000 1:1 ]3Ag o 100.000 122 14-111 Diphcnolic (286) 100, 000 2:1 14-111.- do 100,000 111 The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE I-A.ACYLATED PRODUCTS OF POLYPROPYL- EN EIMINE Molecular Mols of Mols of Wt. of Acid Per Water Ex. Polypro- Acid Mol oi Removed pylenei- Polypro- Per M01 mine p yleneof Acid lmine 15-A1. 2:1 1. 9 15-111. 1:1 1. 1 15-Aa. 1:1 0. 9 Iii-A1. 321 1. U 16-A2. 1:1 1. 2 Iii-A3. 2:1 1. 0 17-A 1:1 2. 0 17-112-. 5,000 0 3:1 1.3 17-11:. 5, 000 Dimeric (600) (Emery 1:1 1. 5

Industries).

18-111-. 10, 000 Diglycolic (134).. 4:1 0.9 18-112. 10, 000 Diphenolic (286). 2:1 1. 0 18A3 10, 000 Naphthenic (330). 121 1. 0 19-111-. 20, 000 Maleic Anhydride (98). 1:1

lit-A7. 20, 000 Nonanoic (158) 4Z1 3. 2 19-113. 20. 000 ic (282) 2: 1 2. 1 20-A1. 40, 000 Myristic (228.4). 2:1 1. 7 220-AL 40, 000 Oleic (282) 3Z1 2. 8 20113. 40, 000 Alkenylwn) Succinic 1:1

Auhydride (266).

OXYALKYLATION Polyethyleneirnine can be oxyalkylated in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octyleue oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions of propylene oxide and ethylene oxide, or smaller proportions thereof in relation to polyethyleneimine. Thus, the molar ratio of alkylene oxide to polyethyleneimine can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 100011, or higher, but preferably 1 to 200. For example, in demulsification extremely high alkylene oxide ratios are often advantageously employed such as 200-300 or more moles of alkylene oxide per mole of polyethyleneimine. On the other hand, for certain applications such as corrosion prevention and use as fuel oil additives, lower ratios of alkylene oxides are advantageously employed, i.e., 1/1-025 moles of alkylene oxide per mole of polyethyleneimine. With higher molecular weight polyethyleneimine, more oxyalkylatable reaction centers are present for alkylene oxide addition and very high ratios of alkylene oxide can be added. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions of oxyalkylation reactions see US. Patent 2,792,369 and other patents mentioned therein.

Oxyalkylation is too well known to require a full discussion. For purpose of brevity reference is made to Parts 1 and 2 of US. Patent No. 2,792,371, dated May 14, 1957, to Dickson in which particular attention is directed to the various patents which described typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jeiferson Chemical Company, Houston, Tex. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The symbol employed to designate oxyalkylation is O. Specifically l-O represents oxyalkylated polyethyleneimine.

In the following oxyalkylations the reaction vessel em ployed is a stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means and the like which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 r.p.m. Polyethyleneimine dissolved and/or suspended in an equal weight of xylene is charged into the reactor. The autoclave is sealed, swept with nitrogen, stirring started immediately and heat applied. The temperature is allowed to rise to approximately C. at which time the addition of the alkylene oxide is started and added continuously at such speed as it is absorbed by the reaction mixture. When the rate of oxyalkylation slows down appreciably, which generally occurs after about 15 moles of ethylene oxide are added or after about 10 moles of propylene oxide are added, the reaction vessel is opened and an oxyalkylation catalyst is added (in 2 weight percent of the total reactants present). The catalyst employed in the examples is sodium methylate. Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, oxyoctylation, oxystyrenation, and other oxyalkylations, etc., the catalyst is added at the beginning of the operation.

Example l-O Using the oxyalkylation apparatus and procedure stated above, the following compounds are prepared: 900 grams (1 mol) of polyethyleneimine 900 in xylene are charged into a stainless steel autoclave, swept with nitrogen, stirring started, and autoclave sealed. The temperature is allowed to rise approximately 100 C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been added over a one-half hour period. This reaction is exothermic and requires cooling to avoid a rise in temperature after removal of xylene. The reaction mass is transferred to a suitable container. Upon cooling to room temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-0 The same procedure as Example 1O is used except that 396 grams of ethylene oxide (9 mols) is added to 900 grams (1 mol) of polyethyleneimine 900. This reaction material is a dark viscous liquid at room temperature.

Example 1-O The same procedure as Example 1-0 is used and 396 grams of ethylene oxide (9 mols) are added to 900 grams (1 mol) of polyethyleneimine 900. After this reaction is completed, the autoclave is opened and 20 grams of sodium methylate are added. The autoclave is then flushed again with nitrogen and an additional 572 grams (13 mols) of ethylene oxide is added at 100 C. This reaction is highly exothermic. The reaction mass now contains 1 mol of polyethyleneimine 900 and a total of 22 mols of reacted ethylene oxide.

Example 1O A portion of the reaction mass of Example 1-O is transferred to another autoclave and an additional amount of EtO was added. The reaction mass now contains the ratio of 1 mol of polyethyleneimine 900 to 40 mols of EtO.

Example 1-O The addition of ethylene oxide to Example 1-O is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 75 mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to Example 1O is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 83 mols of EtO is reached.

Example 1-O7 The addition of ethylene oxide to the Example 1-0 is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 105 mols of EtO is reached.

Example 16-0 2,000 grams (0.1 mol) of polyethyleneimine of molecular weight of 20,000 in xylene are charged into a conventional stainless steel autoclave. The temperature is raised to 120 C., the autoclave is flushed with nitrogen and sealed. Then 11.6 grams of propylene oxide (0.2 mols) are added slowly at 120 C. A sample is taken at this point and labeled 16-0 This sample contains two mols of FIG for each mol of polyethyleneimine. It is a dark, pasty solid at room temperature.

Example 16-0 The addition of propylene oxide to 16-0 is continued as follows: The autoclave is opened and 5 grams of sodium methylate are added. The autoclave is again purged with nitrogen and sealed. Propylene oxide is added carefully until an additional 232 grams have been reacted. A sample is taken at this point and labeled 16-0 This compound now contains 6 mols of propylene oxide for each mol of polyethyleneimine 20,000.

Example 16-0 The oxypropylation of 16-0 is continued until an additional 52.2 grams of propylene oxide are reacted. A sample is taken at this point and labeled 16-0 16-0 contains mols of propylene oxide for each mol of polyethyleneimine 20,000. At room temperature the product is a dark, pasty solid.

This oxyalkylation is continued to produce examples 16-O 16-0 A summary of oxyalkylated products produced from polyethyleneimines is presented in the following Table II.

The Roman numerals (I), (II), and (III) besides the moles of oxide added indicate the order of oxide addition (I) first, (II) second and (III) third, etc.

The following abbreviations are also used throughout this application:

EtO-Ethylene oxide PrOProyplene oxide BuO-Butylene oxide TABLE-II. OXYALKYLATED PRODUCTS [Mols oi alkylene oxide/mol polyethyleneimine] Ex. Mol. Wt. EtO PrO BuO Physical Properties of PE 900 Viscous liquid. 900 Solid. 900 Do. 900 Do. 900 Do. 900 D0. 900 Do. 900 Do. 900 Viscous liquid.

0. Dark, thick liquid.

Do. Do. Do. Do. Do. Do. Do. Do. Do. Viscous liquid.

Do. Solid. 4-04- Do. 5-01. Viscous liquid.

Dark, thick liquid.

Do. Do.

Viscous liquid.

Solid.

Viscous liquid.

Solid.

Do. Do. Do.

Viscous liquid.

Dark, thick liquid.

10 (II) 20 (II) 5 (III) Oetylene oxide, 8 mols Styrene oxide, 5 mols Epoxide 201 (Carbide and Carbon) 1 mol Do. Viscous liquid. Solid.

Do. Viscous liquid.

Solid. Viscous liquid.

I Pasty solid.

Do. Do.

TABLE II.-Continued Ex. Mol. Wt EtO PrO BuO Physical Properties of PE Pasty solid.

Do. 21-0.-.. 50, 000 Epichlorohydrin, 3 mols Do. 22-01-.-- 50, 000 18 (I) 4 4 (III) Waxy solid. 22-07-.-. 50, 000 6 (II) D0. 220 50,000 14 (III) Do. 22-04.-.. 50, 000 (I) Do. 22O5 50, 000 1 (II) D0. 22-00.--- 50, 000 (III) D0. 23-01-.-. 100,000 1 D0. 23-02-.-. 100, 000 5 D0. 23-03-.-- 100, 000 14 Do. 23-04-.-. 100, 000 24 D0. 23O5- 100, 000 48 D0. 23-0 5---- 100,000 60 D0. 23-01--.- 100, 000 75 D0. 23O a 100, 000 150 D0. 24-01-..- Do. 24-01-..- Do. 24-03-." Do. 24-04...- Do. 24-05-... Do. 24-00-..- DO. 24-01.... D0- 24-03.... Do. 24-01---- Do. 24-010--- DO. 25-01.-.. 100, 000 25 (I) Do. 25-011.-.- 100, 000 3 (I) Do. 25-03-.-. 100,000 5 (11) Do. 25O4 100,000 6 (II) D0. 26-01---. 100, 000 8 (III) (I) Do. 26-02-.-. 100, 000 6 (III) (I) 4 (II) Do. 26-03-.- 100,000 5 (II) (I I) 3 (I) Do. 26-04---- 100, 000 15 (II) (I) 6 (III) D0. 26-05.-.- 100,000 2 (I) (II) 2 (III) D0. 26-01..-. 100, 000 4 (I) 14 (III) 6 (II) Do.

The following table presents specific illustration of compounds other than polyethyleneiinine and its derivatives.

TABLE IIA.OXYALKYLATED PRODUCTS OF I POLYPROPYLENEIMINE Mol. Wt. Mols of alkylene oxide per mol of polyof polypropyleneimine Physicgil Ex. propyl- Properties eneimine EtO PrO BuO 27-01. Viscous liquid. 27-02- Do. 27-0 Solid. 27-04 DO. 27-05- D0. 27-05. D0. 28-O1 Viscous Liquid. 28-01 Do. 28-03- D0. 28-04-. D0. 28-05. D0. 28-05. D 0. 28-01- D0. 29-01 Do. 29-01- Do. 29-0 Do. 29-01. Do. 29-01--. 500 Do. [30-01- 500 (I) .10 (II) Do. 30-02- 500 10 (I) 5 (II) Paste. 31-01. 1 500 20 (II) 3 (I) Sol d. 31-01. 500 12 (II) 44 (I) Thick dark liquid 32-01 500 5 (III) 10 (II) Do. 32O1 500 10 (I 40 (I) 3 (III) Do. 32O3 500 15 (I) 80 (II) 1 (III) Do. 32-04- 500 5 (I) 20 (III) 2 (II) Do. 33-0 500 Octylene oxide, 5 mols I Do. 34-0 500 Styrene oxide, 3 mols Do. 35-O 500 Epoxide 201 (Carbide and Solid. 1 Carbon) 1 mol 36-01- 1, 000 Viscous liquid. 36-01. 0. 36-0 Solid. 36-04- Do. 36-0 Do. 36-0 5. D0. 36-01- Waxy solid. 37-01 Viscous liquid. 37-0 Do. 37-0 Do. 37-04 D0. 37-0 Do. 38-0 Do. 38-01- olid. 39-01- Viscous Liquid. 39-02 0. 39-0 Solid.

TABLE II-A.C0ntinued Mol. Wt. Mols of alkylene oxide per mol of polyoi polypropyleneimine Physical Ex. propyl- Properties eneimine EtO PrO BuO 39-10 1, 000 10 (II) 10 (III) 10 (I) Thick liquid. 40-0--.. 1, 000 Epox de 201 (Carbide and Solid.

Carbon) 2 mols 41-0 1, 000 Styrene oxide, 6 mols Viscous liquid. 42-0 1, 000 Octylene oxide, 2 mols Do. 43-01---- 5, 000 1 D0. 43-02.-.- 5 D0. 43-0 20 Solid. 43-04--.- 45 Do. 43-05-.. 75 Do. 43-011-... Do. 44-01-. Viscous liquid. 44-01--.. Thick liquid. 44-03-..- D0. 44-04--.- D0. 44-05.-.. D0. 44-00-..- D0. 44-07--.- DO. 45-01---. Viscous liquid. 45-01-. Do. 45-03-..- D0. 45-01-- Do. 46-01-..- Do. 46-02.... D0. 46-0 Do. 46-01-... Do. 46-0 D0. 46- 5..-. D0. 47-0 Do. 48-01.-.. Pasty solid. 48-01"- Do. 48-03.... D0. 48-04--.. D0,. 48-05--.. Do. 49-01-..- D0. 49-02..-. Do. 49-03-..- D0. 49-04.-.. Do. 5001.. DO. 50-01--.. Do. 50-03---. D0. 51-01..-. D0. 51-02--.- D0. 51-03---- D0. 51-04-.-. D0. 52-0. Do. 53-0- Do.

54-01--. Waxy solid. 54O2 D0. 54-03.... D0. 50-04--.- D0. 54-0 D0. 55-01-... D0. 55-02..-- D0. 55-03.--. D0. 55-04---- D0. 55-O5 D0. 55-00.--. Do. 56- 1..-- D0. 56-02--.- D0. 56-0 Do. 56-04.-.. D0. 56-05..-- D0. 56-011.--. Do. 57-01..-- DO. 57-02.-.. Do. 57-03.-.. Do. 57-04.. D0. 580i..-- D0. 58-02..-- D0. 58-03..-- D0. 58-04---. Do. 59O1 Do. 59-02---- Do. 59-03--.- D0. 59- 4..-. Do; 59-0 D0. 60-01--.. DO- 60O1.-- Do. 60-03..-. D0. 60-0 Do. 61-01.--- D0- 61Oz D0. 61-03.... D0. 61-04--.. D0. 62-O Do. 62-01-.-. Do.

ACYLATION THEN OXYALKYLATION Prior acylated polyethyleneimine can be oxyalkylated in the above manner by starting with acylated polyethyleneiinine instead of the unreacted polymer. Non-limiting examples are presented in the following tables. The symbol employed to designate an ,acylate, oxyalkylated polyethyleneimine is AO. Specifically 1A O represents acylated, then oxyalkylated polyethyleneimine.

Example 1-A O For this example an autoclave equipped to handle alkylene oxides is necessary. 1671 grams (1 mole) of 1A are charged into the autoclave. Following a nitrogen purge and the addition of 75 grams of sodium methylate, the temperature is raised to 135 C. and 2436 grams of PrO (42 mols) are added. At the completion of this reaction, 440 grams of E0 mols) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent. Ratio of reactants, 1 mole starting material/Pro 42 mols/EtO 10 mols.

' Example 2A O TABLE III.--OXYALKYLATED, PRIOR ACYLATED POLY- ETHYLENEIMINE [Mols of oxide per mol of reactant] Example EtO PrO BuO Physical Property 1-A5O1 Viscous liquid. 1AsO2..- D0.

111503.. 10 DO. 1A504 14 (III) 26 (II) 10 (I) Do. 1-A5O5... 4 (I) 12 (II) go.

0. Dark, viscous liquid. Solid. Thick liquid.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IIIA.-OXYALKYLATED, PRIOR ACYLATED POLYPROPYLENEIMINE Example EtO PrO BuO Physical Property A2O1. 10 Viscous liquid. 15Az02.. 3 Do. 15A2Oa.- 2 (I) 2 (II) Do. 15AzO4. 6 (II) 10 (I11) 2 (1) Do. 15A2O5 4 Do. 16"A10...-.- Epoxide 201 (Carbide and Do.

Carbon), 1 mol 17Aa01.. 10 (II) 80 (I) Do. 17-A302... DO- 18-AaO1. 3 Pasty solid. 18AsO2- Octy en ox e, ols 18113014.-.- 20 (11) l 5 (I) Do. 1811304.... D0. 19-11301. Styrene oxide, 3 mols Do. 194.301.--. 5 (III) 40 (II) 2 (I) Do. 19-11 03- 12 (II) 65 (I) Do. 204 01. Epichlorophydrin, 2 mols Do. ZO-ArOz. D0- 20A103 3 D0.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated polyethyleneimine can be acylated with any of the acylation agents herein disclosed (in contrast to acylation prior to oxyalkylation). Since these reactants also have hydroxy groups, acylation, in addition 16 to reaction with amino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried out with polyethyleneimine itself, i.e., dehydration wherein the removal of water is a test of the completion of the reaction.

Example 1O A Example 2O A 0.1 mole of 2-0 (380 grams) in 400 ml. of xylene is mixed with 0.1 mole of palmitic acid (25.6 grams) at room temperature. Ratio 1 mole 2O to 1 mole of palmitic acid. Vacuum is applied and the temperature is raised slowly until one mole of water (18 grams) is removed. This product is a dark viscous liquid.

Example 2-O A 0.1 mole of 2-0 (757 grams) is mixed with 500 grams of xylene and heated to C. 0.1 mole of digiycolic acid (13.4 grams) is added slowly to prevent excessive foaming. Ratio 1 mole 2-0 to 1 mole glycolic acid. The temperature is raised to -150" C. and held until one mole of water has evolved. This product is the diglycolic acid fractional ester of 2-0 A white precipitate forms during this reaction which can be removed by filtration. Analysis shows the precipitate to be sodium acid diglycollate, a reaction product of the catalyst and diglycolic acid. The filtered product is a dark viscous liquid at room temperature.

Table IV contains examples which further illustrate the invention. The symbol employed to designate oxyalkylated, acylated products is 0A.

TABLE IV.-AGYLATED, PRIOR OXYALKYLATED POLY ETHYLENEIMINE Ratio mols of Mols of acylwater re- Ex. Acylating ating agent moved to Physical Agent per mol oxymols acylat- Properties alkylated ing agent employed 1-O1A1-.. Acetic 3 1 Dark viscous liquid. 1OrAr--- 1 1 o. 1OaA... 2 1 Solid. 2O3A 3 1 Do. 2-0.1 m 1 1 Do. 2-O6A. Diglycollc. 1 1 Do. 4OzA Stearic 2 1 Do. 6-O1A Maleic an 1 Viscous liquid.

12-0211-" 2 1 Do. lit-03A.-. 1 1 Do. 14-OiA... 2 1 Do. 15-0 11--- 1 1 Do. lift-05A. 1 1 D0. 17OaA 1 2 Do. 18-0511-" 2 1 Do. 19-0111... Ricinoleic 1 1 D0. 20-0511... Maleic anhy. 1 Do.

dride. 22-0511. Linoleic 3 1 Do. 23O2A Palmitic 1 1 Do. 241-0411... Acetic 1 1 Do. 25O3A1 Dimerio 1 1 Solid.

(Emery Indus). 25O:4Az Diglycolie. 1 1 Do. 26O1A Dipheno1ic.. 1 1 Do. 26-0511... 'Ierephthaiic" 1 1 Do. 26OA- Benzoic 1 1 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IVA.AOYLATED, PRIOR OXYALKYLATED POLY.

PROPYLENEIMIN E Ratio mols of Mols of aeylwater re- Ex. Acylating ating agent moved to Physical Agent per mol oxymols aeylat- Properties alkylated ing agent E employed 27OzA Oleic 2 2 Thick dark liquid. 27-O A.-. Diphenolic 1 1 Pasty solid. 28OaA L 3 1 Do. 28-O0A--. 4 1 D0. 29-O2A.. l 1 D0. 31-0 Stearic 2 2 Do. 32-04A.-. Tall oil 1 1 Do. 37-01 Maleic l Do.

anhydride. 39O2A-.- Palmitic 2 2 D0. 4300A.. Dimeric 3 1 Waxy solid.

(Emery industries). 440 A Diglycolic 1 1 Pasty solid. 45-0 11- Myristic 2 1 Do. 48-0 Ricinoleic 1 1 Do.' 50O-. A Abietic 2 2 Do. 5l-O A Linoleic 1 1 Do. 57O A N onanorc 1 1 Do. 59-O A- Laurie. 1 1 Waxy solid 62-02A.--- Diglycolie 1 1 Do.

HEAT TREATMENT OF OXYALKYLATED PRODUCTS The oxyalkylated products described herein, for example, those s'hown in Table II relating to oxyalkylated polyethyleneimine and those in Table HI relating to oxyalkylated, prior acylated, polyethyleneimine can be heat treated to form useful compositions.

In general, the heat treatment is carried out at 200- 250" C. Under dehydrating conditions, where reduced pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example 150-200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/or reduced pressure can be used to facilitate water removal.

The exact compositions cannot 'be depicted by the usual chemical formulas for the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is effected by heating same at elevated temperatures, generally in the neighborhood of ZOO-270 C., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile distillate usually contains Water formed by reaction. The water can be separated from such condensed distillate by any suitable means, for instance, distilling with xylene, so as to carry over the water, and subsequently removing the xylene. The dried condensate is then returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a high-boiling solvent, which is permitted to distill in such a manner as to remove the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the original reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the water of reaction is removed from the combining mass. Polymerization can be effected Without the use of catalysts in some instances, but such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and usually a significantly higher temperature. The use of catalyst such as iron, etc., fosters the reaction.

The following example are presented to illustrates heat treatment. The symbol used to designated a heat treated oxyalkylated polyethyleneimine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material are employed.

Example 2O H A conventional glass resin vessel equipped with a stirrer and water trap is used. Five hundred grams of 2-0' are charged into the above resin vessel along with five grams of CaCl The temperature is raised to 225-250 C. and heated until 57 grams of Water (3.2 mols) are evolved. This process takes 7.5 hours of heating. The product is an extremely viscous material at room temperature. However, upon warming slightly this product dissolves easily in water.

Example 19-O H The process .of the immediately previous example is repeated using 19-0 but substituting sodium methylate for calcium chloride. The product is a dark, viscous, water-soluble material.

Example 15O H The process of Example 2O H is repeated using 15-0 but substituting powdered iron from calcium chloride.

TABLE V.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED POLYETHYLENEIMIN E Water Removed Example Reaction Catalyst (5 grams) Tune in Physical properties -Temp., hours C. Grams Mols 250 Iron 74 4v 1 8. 0 Dark, viscous liquid. 225 CaCl 57 3. 2 16.5 Do.

265 Sodium methylate 36 2. O 23 Do. 270 03011 38 2. l 30 Do. i 95 5. 3 9. 5 Solid.

32 1. 8 12 Viscous liquid. 40 2. 2 13 D0. 72 4 18 D0. 54 3 24 D0. 5 30 Do. 54 3 16 D0. 36 2 18 D0. 76 4. 2 20 Solid. 54 3 16 Viscous liquid. 63 3. 5 8 Do. 57 3. 2 12 D0. 36 2 14 D0. 38 2. l 11 Do. 40 2. 2 13 D0. 36 2. O 16 Paste. 40 2. 2 8 D0. 90 5 14 D0. 32 1. 8 18 D0.

amines, alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the TABLE VA.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED,

OXYALKYLATED POLYPROPYLENEIMINE Water Removed Example Reaction Catalyst (5 grams) Time in Physical properties Temp., hours C. Grams Mols 32 1. 8 18 Dark, viscous liquid.

54 3. 0 24 Pasty.

40 2. 2 13 Viscous liquid.

ALKYLATION Alkylation relates to the reaction of polyethyleneimine and derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; tbutyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; decosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of monochlor-owax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and polyethyleneimine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. For certain uses it is preferable to carry out the reaction at temperatures of between about 100 and about 250 C., preferably between about 140 C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for example, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl alkyl halide reactant and polyethyleneimine in a hydrocarbon solvent under reflux conditions. The aromatic hydrocarbon solvents of the benzene series are especially preferable. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued until no more hydrogen halide is formed. In general, the time of reaction will vary widely, such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and polyethyleneimine results in the formation of products where the alkyl group of the alkyl halide has replaced a hydrogen atom attached to a nitrogen atom. It is also conceivable that alkylation of an alkylene group of polyethyleneimine can occur. However, the eaxct composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of polyethyleneimine 900, a mixture of mono-, diand tri and higher N-alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in different molecules of polyethyleneimine.

Thus, the term Alkylation as employed herein and in the claims include alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the polyethyleneimine at the desired ratio in the persence of one equivalent of base for each equivalent HCl given off during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, no base is added.

The following examples are presented to illustrate alkylation of polyethyleneimine.

In these examples, the term mesomer is employed. A mesomer is defined as a repeating radical which, when tion of the polymer molecule.

Thus, the unit forms the principal por- I I H CON-- H H I is the mesomer of polyethyleneimine, since polyethyleneimine may be represented by the formula Example K 430 grams of polyethyleneimine 50,000, equivalent to mesomeric units of ethyleneimine, in 500 ml. of xylene and 570 grams of sodium carbonate, equivalent to 8 moles, are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser take-01f for removal of volatile components. The stirred reactants are heated to about 100 C. whereupon 1140 g. (8 mols) of dichloroethyl ether is started in slowly at such a rate that the temperature of the reaction vessel contents never exceeds 165 C., but preferably stays around 135 C. The reaction is exothermic and 5-6 hours are required to add all the dichloroethyl ether. After all the dichloroethyl ether has been added, the temperature is allowed to drop to about 90-100 whereupon reduced pressure is applied to the reaction vessel and all xylene stripped out. The material left in the vessel is a thick brown liquid which solidifies upon cooling to a glassy-solid.

Example 8-A The equivalent of 8 mesomeric units, based on polyethyleneimine, of the material 8-A (Table 1) in 300 g. xylene is placed in a reaction vessel described in the above example for 5K 340 grams anhydrous sodium carbonate, equivalent to 3.2 moles are added followed by 1.6 moles dimethyl sulfate. The temperature is then brought up to 125 C. and held there for a period of 6-8 hours. Xylene is then removed under reduced temperature and pressure conditions as in the example for 5-K The resulting product, a dark amber material, is very viscous at ordinary temperature.

Example 20O HK The equivalent of 10 mesomeric units based on polyethyleneimine of the materials 20O H (Table V) in 300 ml. of Xylene and 420 grams sodium bicarbonate, equivalent to 5 moles, are placed in an autoclave equipped with a stirring device, a thermometer and a condenser reflux device which can be closed off from the autoclave during reactions in which pressures above atmosphere are experienced. The autoclave is closed and heat is applied to bring up the temperature to 120- 130" C. at which time 5 mols methyl chloride are added slowly while never allowing pressure to exceed 5 atmospheres pressure. Several hours will be necessary to .get all methyl chloride in and pressure inside the vessel down to one atmosphere. At this point the reflux condenser is opened, the temperature is allowed to drop to 90-100 C. and a slight vacuum applied in order to reflux the xylene out of the autoclave. The resulting material is a very viscous amber colored liquid.

The reactions shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two ways-(1) in the presence of base, as in 5-K to yield the alkylation product and (2) in the absence of base to yield the halogen-containing or sulfatecontaining (S-K X) products.

The alkylated products of this invention mary, secondary, tertiary, and quaternary amino groups. By controlling the amount of alkylation agent employed and the conditions of the reaction, etc., one can control the type and amount of alkylation. For example, by reaccontain pri- 22 tion less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen-bonded hydrogen present on the molecule and by exhaustive alkylation in the presence of suflicient basic material, one can form more highly alkylated compounds.

The moles of alkylating agent reacted with polyethyleneimine will depend on the number of alkylation reactive positions contained therein as well as the number of moles of alkylating agent one Wishes to incorporate into the molecule. Theoretically, every hydrogen bonded to a nitrogen atom can be alkylated. We have advantageously reacted 1-20 moles of alkylating agent per moles of polyethyleneimine 900 but preferably 1-412 moles. With polyethyleneimine 20,000 greater amounts of alkylating agent can be employed, for example l-SO moles, and with polyethyleneimine 40,000, l-l00 moles, etc. Optimum alkylation will depend on the particular application.

In addition, the alkyl halide may contain functional groups. For example, chloroacetic acid can be reacted with polyethyleneimine to yield a compound containing carboxylic acid groups.

PNCH COOH, wherein P is the residue of eneimine.

In addition, polyethyleneimine can be alkylated with an alkyl halide such as alkyl chloride and then reacted with chloroacetic acid to yield an alkylated polyethyleneimine containing carboxylic acid groups polyethyl- 0 I2 Z5 N )n P(CH2gOH) The symbol employed to designate an alkylated polyethyleneimine is K. Where the product is a salt or a quaternary the symbol is KX. Thus, for example, where no acceptor base is employed and a salt is allowed to form 1-A O K would be 1A O KX.

TABLE VI.ALKYLATED PRODUCTS Mols Mol. alkylating Physical Example Wt. Alkylating agent agent per properties PE mesomer unit 900 Allyl chloride 0. 2 Viscous liquid. 900 do 0.7 Do. 900 Benzyl chloride 0.3 Do. 900 do 0.8 Solid. 5, 000 Methyl chloride---" 0.3 Viscous liquid. 2-K, 5,000 d0 1.0 Solid. 2-K3 5, 000 Ethylene dichloride 0. 2 Viscous liquid do 0. 5 Do. 1,4'dichlorobutene-2 0. 2 Do. do 0.5 Do. Dimethyl sulfate O. 2 Do. do 0. 4 Do. Dodecylbenzene 0. 2 Solid.

chloride.

.do D0 0 Butyl chloride 0.5 0. 3 Viscous I liquid. do 0. 6 Do. Dichlorodiethyl 0. 2 Do.

ether. 5-K, 50, 000 do 0.8 Solid. 5-K 0, 000 Benzyl ehloride.- 0.3 Viscous liquid. 5-K 50, 000 do 0.8 Solid. 6-K1 100, 000 Ethylene dlchloride 0. 2 Viscous liquid. 100, 000 do 0.8 Do. 100, 000 Methyl chloride 0. 3 D0. 100, 000 do 1. 0 Solid.

1,4 xylidene chloride 0. 2 Viscous liquid. do 0.2 Do. Dodecenyl chloride 0. 2 Solid. Methyl chloride 0. 5 Viscous liquid. Benzyl chloride. 0. 4 Solid. Dimethyl sullate 0. 2 Viscous liquid. Dichlorodiethyl 0. 4 Do.

ether. 1,4-diehlorobutene-2. 0. 3 Do. Benzyl chloride 0. 4 Solid. Methyl ehloride 0.7 Do.

Ethylene dichloride- 0. 2 Viscous liquid Benzyl chloride. 0. 4 Solid.

TABLE VI.Con'tinued TABLE VI-A.Con tinued Mols Mols M01. alkylating Physical M01. alkylatirig Physical Example Wt. Alkylating agent agent per properties Example Wt. Alkylating agent agent per properties PE mesomer PE mesomer unit unit 11-O2K Dimethyl suliate. 0.2 Viscous 27-0zAK Dichlorodiethyl 0.2 Solid.

liquid ether. 14OiK Dichlorodiethyl 0.4 Solid. Di1nethylsulfate..-. 1.0 Do. ether. Methyl chloride" 0.8 Do. Iii-04K Methyl chlorlde-...- 0.6 Do. Allyl chloride 0.5 Do. 19-02K Dodecyl benzyl 0.2 Do. 20A1OtHK Butyl chloride 0.2 Do.

chloride. 1,4 xylylene di- 0. 2 Viscous chloride. liquid Benzyl chloride. 0. 5 Solid.

Methyl chloride. 0. 6 Do.

Dodeeenyl chloride 0. 2 Do.

Ethylene dichloride. 0.3 Viscous In addition to the above examples wherein a base liquid 14 dicmombutene 2 0.2 acceptor lS employed to remove the acid anion such as Benzylchloride.- 0.4 Solid, halogen, sulfate, etc., the above examples are also preg pared omitting the inorganic base from the reaction Methyl chloride.-. 0.5 Do. medium. When this is done, a halogen containing salt, ggg gi gg gg gg g-i B3 quaternary, etc. is formed. Examples where such salts Dichlorodiethyl.... 0.3 vilscousl are formed will be designated as above except that they (L6 will contain an X designation for example lnstead of Benyl chloridc 0.2 So]l)id. 1O A K they will be 1O A KX, and instead of 22-O AK DichlorodiethyLnu 0.2 viscous 25 they will be 22-O AKX, etc. X indicates salt formaether. liquid 121011.

Ethylene dichloride- 0. 2 Do.

Methyl chloride. 0.5 Do. 25-OzHK..-. Dimethyl suliate o. 2 Do. ALKYLATED THEN ACYLATION The alkylated material prepared above can be further The following table presents specific illustration of treated with acylating agent where residual acylatable compounds other than polyethyleneimine and its derivaamino groups are still present on the molecule. The tives. acylation procedure is essentially that described above wherein carboxylic acids react with the alkylated poly- TABLE VI A ACYLATED PRODUCTS ethyleneiniine underdehydrating conditions to form amides and cyclic amidines. The product depends on the ratio of moles of water removed for each carboxylic 'd ro e 1 mole Water/ 1 mole carbo lic e se tial Mol. alkylating Physical acl Xy s n Example Wt. Alkylating agent agent per properties ly amides; more than 1 mole water/1 mole carboxylic PE mmmm 0 acid grou essentiall c clic amidines, such as imadazounit y y hnes.

Allyl chloride 2 vispoqs Such compounds are illustrated in the following table. d 0 7 q The symbol employed to designate alkylated, acylated g g gg g 3 8: products is KA and acylated, alkylated, acylated prod- .....do 0.8 Do. ucts is AKA,

Methyl chloride...-. 0.7 Do.

.. ..do 1.0 Do.

28: TABLE VII.-AOYLATED, PRIOR ALKYTIATED POLY- Q2 ETHYLENEIMINE OR DERIVATIVE irne y su a e.... .2 o.

chlogde Example agent agent per mole properties d0 5 Do. mol PE reactant Butyl chloride- 0. 3 Do.

gf ga y 1-KaA Laurie 4:1 1 vilsicoluis1 ..-..do 0.8 Do. 15

Benzyl chloride. 0.3 Do. 1 D

Metgyl chlonde' 3g Nonanoic.. 221 1 Viscous liquid.

Allyl chloride. 0. 5 Do.

Diniethyl sulfate... 0.8 Viscous gg tg%g 8 hqmd anhydride Methyl chloride....- 0.3 Do. alkyl Ethylene dichloride. 0.8 Do. (0 2) Di ilil10f0dlethyl 0.2 Solid. 5 K4A 1 5 solid e ier. I

- ic oro uteneo.

Dodecenyl chloride. 0.5 Viscous 6 g gfy gfia: g8:

. Laurie 211 1 Do.

Benzyl chloride.-. 0.2 Do. 0161c 0 L3 D0 f g dlchlO- 1-o.HKA Maleic 11-" 1:1 Solid.

Dodeeyl benzene 0. 8 Do. hydnde chloride.

Dimethyl sulfate... 0. 3 Solid Ethylene dichloride. 0.7 Do.

Butyl chloride 0. 2 Do.

Allyl chlo"ide.- 0. 5 V Do.

Benzyl The following table presents specific illustrations of 15-A04K---- Methy ch or e Solidcompounds other than polyethyleneimine and its deriva- 19-A3O1K... Ethylene dichloride. 0. 6 Do. 19-A303K Dichloro pentane.-.. 0. 5 Do.

TABLE VIIA.ACYLATED, PRIOR ALKYLATED POLY- PROPYLENEIMINE OR DERIVATIVE Ratio mols Mols of water Acylating of aeylating removed per Physical Example agent agent per mol of properties mol PE reactant deriv.

2:1 1 Viscous liquid 2:1 1 Do. 1:1 1 D0. 2:1 1 D0. 2:1 1. 3 D0. Maleic an- 1:1 Solid.

hydride. Laurie 4:1 1 Viscous liquid Oleic 1:1 1. 6 Do. Pahnitic 1:1 1 D0. Dimeric. 0. 5:1 1 Do. Nonanoic- 2:1 1 Do. Ricinoleic 2: 1 1. 8 Do;

2:1 Solid succinic anhydride (C-12). 44O AKA- Stearic 1:1 1 Viscous liquid. 46O HKA Myristic 2:1 1 Do. 20-A OzHKA Acetic 1:1 1 Do.

OLEFINATION Olefination relates to the reaction of polyethyleneimine and derivatives with olefins.

The compositions of this invention, including polyethyleneimine itself as well as reaction products thereof containing active hydrogens, can be reacted with unsaturated compounds, particular compounds containing activated double bonds, so as to add polyethyleneimine across the double bonds as illustrated herein:

Where the compound contains an additional active hydrogen, other unsaturated molecules can be added to the original molecule for example Where one or more active hydrogens are present at another reactive site, the following reaction could take place:

The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner & Zook (Wiley 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives thereof including the following-acrylonitrile, acrylic and methacrylic acids and esters crotonic acid and esters, cinnamic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, polyethyleneimine and derivatives thereof containing active hydrogens can be used to prepare telomers of polymer prepared from vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no water is eliminated. The reaction is relatively simple, as shown by the following example:

Charge 900 grams of polyethyleneimine 900 in xylene (1 mol) into glass resin apparatus. Care should be taken that the PEI 900 is water-free, to eliminate undesirable side reactions. At room temperature, slowly add 53 grams of acrylonitrile (1 mol). The reaction proceeds smoothly Without the aid of a catalyst. Warm gently to -100 C. and stir for one hour.

Example 6-U To 1,000 grams of polyethyleneimine 100,000 (0.01 mols) in 300 grams of xylene, add 1.24 grams of divinyl sulfone (0.01 mol) at room temperature. This reaction is exothermic and the ambient temperature is employed.

Example 2O KAU Same reactions as Example l-U except that 1 mol of methyl acrylate is substituted for acrylonitrile and 2O KA is substituted for the polyethyleneimine 900. Part of this product is thereupon saponified with sodium hydroxide to form the fatty amino acid salt.

Further examples of the reaction are summarized in the following table:

TAB LE VIIL-O LE FINATION Example Mol. polyethyleneirnine wt. of Mols of olefin per mol PE Acrylonltrile- Methylacrylat Ethyl crotonate- Dioctyl meleate.-- Divinyl sulfone. Styrene Lauryl methacrylate Divinyl sulfone. Methyl methacrylate Acrylonitrile Divinyl sulfon Ethyl crotonate. Dioetyl maleate HHHHHHHHHHHHHHHHHP- TABLE VIII.-Cn-tinued Mols of Example Olefin olefin per Time Temp., 0

mol PE Styrene 1 1 90 Divinyl sulione 1:1 Methylaorylate 1:1 -100 Divinyl sulfone 1 1 70 Styrene 3:1 Dimethyl maleate. 1 1 Dloetyl ma1eate. 2:1 100 Ethyl erotonate. 2:1 125 Divinyl sulfone 1: 1 70 Styrene 4: 1 90 Acrylonitrlle. 3 1 80-100 Methylaerylate. 3 1 80-100 Acrylonitrile 3:1 80-100 Methyl methaerylate. 1:1 80-100 Divinyl sulfone 1 1 70 Lauryl ruethaerylate. 2:1 135 Divinyl sulione. 1: 1 70 Dioetyl maleate. 2:1 100 Ethyl erotonate. 2:1 125 Ethyl ciunamate 2:1 Styrene 3:1 90 Methylaerylate 2:1 80-100 Aerylonitrile 1:1 80-100 The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

and other isomeric configurations, such as where the Schiffs base is present on the non-terminal amino group rather than on the terminal amino group, etc.

TABLE VIIIA.-OLEFINATION OF POLYPROPYLENEIMINE Mols of Molecular olefin per Time Example wt. of poly- Olefin mol of Temp,

propylenepolyprohours C.

imine pyleneumne 500 Styrene 1:1 1 90 Divinyl sulfone. 1:1 1 70 Acryl0nitrile 2: 1 1 80-100 1:1 2 120 1:1 1 110 3:1 2 1:1 3 1:1 3 120 4: 1 1 80-100 10,000 Styrene 2:1 1 90 10,000 Divinyl sulfone 1:1 1 80 10, 000 Methylacrylate 2:1 1 100 20,000 Lauryl methaerylate 1:1 3 110 20, 000 Styrene 2: 1 1 90 20, 000 Divinyl sulfone 1:1 1 80 40, 000 Methyl acrylate. 2:1 2 120 40, 000 Acryl0nitrile 3:1 1 80 40, 000 Dioctyl maleate 1:1 4 110 CARBONYLATION A wlde variety of aldehyde may be employed such as Carbonylation relates to the reaction of polyethylene- Where primary amino groups are present on the polyethyleneimine reactants, Schiffs bases can be formed on reaction with carbonyl compounds. For example, where an aldehyde such as salicylaldehyde is reacted with polyethyleneimine 900 in a ratio of 2 moles of aldehyde to 1 mole of PE 900, the following type of compound could be formed:

Lesser molar ratios of aldehyde to polyamine would yield mono- Schiffs base such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., in-

imine and derivatives thereof with aldehydes and ketones 50 eluding Substituted derivatives Such as those containing aryloxy, halogen, heterocyclic, amino, nitro, cyano, carboxyl, etc. groups thereof. Non-limiting examples are the following:

Aldehydes Benzaldehyde 2-rnethylbenzaldehyde 3-met-hylbenzaldehyde 4-methylbenzaldehyde Z-methoxybenzaldehyde 4-methoxybenzaldehyde a-naphthaldehyde b-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyde n-Butyraldehyde He-ptaldehyde Aldol Z-hydroxybenzaldehyde 2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3 -methoxybenzaldehyde 2-4-dihydroxybenzaldehyde 2-6-dihydroxylbenzaldehyde Z-hydroxynaphthaldehyde-1 1-hydroxynaphthaldehyde-2 29 A ldehy des.Conti-nued Anthrol-Z-aldehyde-l 2-hydroxyfiucreme-aldehyde-1 4-hydroXydiphenyl-aldehyde-3 30 I In addition to increasing the molecular weight by means of aldehydes, these compounds result in the forma tion of cyclic compounds. Probably both molecular weight increase and cyclization occur during the reaction.

The following examples illustrate the reaction of carigfii gifii 3532 52352; 2 3 523 22: bonyl compounds with polyethyleneimines. The symbol 2 y i 5 zhlorobenzalgehyde employed to designate carbonylation is C, acylation,

a n L: ,9 dmxys: 5 dibromobenza1 dehy dc carbonylation AC, and alkylation, carbonylatlon KC. 2-hydroxy-3-nitrobenzaldehyde Examples 1 2'hYdrOXY3cyanobenzaldfhyfiied Charge 900 grams of polyethyleneimine 900 and 900 de y e grams of Xylene into a conventional glass resin apparatus 4-hydroxypyr1d1I1eald y fitted with a stirrer, thermometer and side-arm trap. Raise 4'hydroxyqulnoline'aldafiyde'g temperature to 90 C. and slowly add 44 grams of 7-hydr0Xyqu1nol1ne-alde yde-S 15 acetaldehyde (1 mol). Hold at this temperature for three formaldehyde hours. Vacuum is then applied until all xylene is stripped glyoxal 011. The reaction mass is a thick dark liquid which is glyceraldehydg soluble in water.

Schifls bases are prepared with the polyethyleneimines Example 5-C of .i invintlon a convffnuonal P Such as Using the same apparatus as above, charge 500 g. sewed SYPthem Organ: Chemlstry by Wagni" & 0.1 of polyethyleneimine 5,000. While stirring, add 2001((1953 W11ey)page 3. 1 d th slowly at room temperature 8.2 grams of 37% aqueous Whfire more extreme con moms formaldehyde (0.1 mol of HCHO). After the reaction products.may be moreponiplex Wherem t car Ony has ceased, raise temperature to 100 C. The reaction reactant 1nstead of reacting ntramolecularly 1n the case mass may be stopped at this point. It is a viscous water of a sghlf? 5 base may react mtermolecularly so as to soluble material. However, it is possible to continue heatas bndgmg means between Y or more polyethylene lm' ing under vacuum until all of the water has been elimme compounds thlls .mcreasmg molecular Welght inated. Cross-linking occurs with this procedure and care of the polyethyleneimine as schematically shown below must be taken topreventinsolubflizationl in the case where formaldehyde is the carbonyl compound: Further examples of this reaction are Summarized in (cH P) )H the following table:

TABLE IX.CARBONYLATION Mol ratio M01. wt. of aldehyde to Temp., polyethyl- Aldehyde polyethyl- C. Time 7 eneimme eneimine or deriv.

900 Acetaldehyde 1:1 3hours 900 do 2:1 90 Do. 900 do 3:1 90 Do. 5,000 Heptnldehyde. 5:1 4hours 5,000 do 3:1 125 Do. 5,000 "H-001. 1:1 125 Do. 11,500 Glyoxal 2:1 80 11mm 11,500 d0 1:1 80 Do. 11,500 0.. 05:1 80 Do.

,000 Salicylaldehyde 0:1 140 3hours 20,000 d0 5:1 140 Do. 20,000 do 3:1 140 Do. 50,000 Formaldehyde 3:1 (1) lhour. 50,000 do 2:1 (1) Do. ,0 ...do. 2:1 (1) Do. 100,000 Glyoeraldehyde 0:1 125 5h0nrs 100,000 3:1 125 Do. 100,000 ...do 2:1 125 Do. 100,000 Salicylaldehyde 3:1 120 2hours 100,000 do 2:1 120 D0. 100,000 1:1 120 Do. 100,000 Benzaldehyde 3:1 110 lhour 100,00 1o 2:1 110 Do.

Mol ratio Example Aldehyde aldehyde to Temp., Time polyethyl- C,

eneimine Benzaldehyde. 1:1 110 lhoul. Glyoxal 3:1 100 2hours. do 2:1 100 Do. do 1:1 100. Do. Formaldehyde- 3: 1 (2) 1 hour. do 1. 2:1 (z) o. .do 1:1 (2) 0. Glyceraldehyde 3:1 4hours. d 2:1 130 o. Furfuraldehyde 3:1 100 lhour. do 2:1 100 Do. .-do 1:1 100 Do. Heptaldehyde. 3:1 61101115. do 2:1 140 Do. do 1:1 140 Do. Formaldehyde. 3:1 (2) 1 hour. d0 2:1 (2) Do. do 1:1 (2) Do.

- 1 Start at 25 C.; raise to 100 C -Start at 25 C., raise to 90 C TABLE IX-A.CA RBONYLATION Mol. wt. of M01. ratio Example polypropyl- Aldehyde aldehyde to Temp., Time in eneimine polypropyl- 0. Hours 7-01 500 Benzaldehyde... 1:1 110 lhour 7-0, 500 ..do 2:1 110 Do 7-03 500 do 3:1 110 Do 8-01 1,000 Salicylaldehyd 4:1 120 Do. 8-01 1,00 .....de 3:1 120 Do. 8-03 .(lo 2:1 120 Do. 9-0 5,000 Formaldehyde 2:1 90 Do. 9-0, 5,000 ...do. 2 1:1 90 Do. 9-03 5,000 do 1 :1 90 Do. 10-0 10,000 Glyoxal 2:1 00 Do. 10-01 10,000 0.. 1:1 90 Do. 10-0 10,000 do 05:1 90 Do. 11-01 20,000 Aoetaldehyde 3:1 100 2hours 11-0, 20,000 do 2:1 100 D0 11-03 1:1 100 Do 12-C1 4:1 130 8 hours 12-0; 3:1 130 Do 12-03 2:1 130 Do Mol ratio of aldehyde to Temp, Time in Example Aldehyde polypropyl- 0. hours eneimme or derivative Glyeeraldehyde 3: 1 125 4 Heptaldehyde 2: 1 125 4 Furfuraldehyde 1: 1 100 2 Glyoxal 1:1 90 1 B enzaldohyde 4: l 120 2 Formaldehyde. 1: 1 1 1:1 100 2 1 Start at 0., raise to 100 C.

The above table presents specific illustration of com- Example designation: Meaning pounds other than polyethyleneimine and its derivatives. (17) OK Oxyalkylated, then alkylated.

The examples presented above are non-limiting exam- (l8) OKX Salt or quaternary of (17). ples. It should be clearly understood that various other 0 (19) C Carbonylated. combinations, order of reactions, reaction ratios, multi- (20) AC A l t d, th carbonylated, plicity of additions, etc., can be employed. Where addi- (21) KC Alkylated, then Carbonylated. tional reactive groups are still present on the molecule, (22) CO c b l t d, th xyalkylthe reaction can be repeated wlth elther the original red, actant or another reactant. (23) U Olefinated.

The type of compound prepared as evident from the (24) AU Acylated, then olefinated. letters assigned to the examples. Thus, taking the branched (25) KU Alkylated, th 1 fi t polyamine as the startinglmaterlal, the following example (26) KUX s l or quaternary f 25 deslgnatlons have the 0 Owmg meamng' In addition to polyethyleneimine itself, other polyalkyl- Example designation: Meaning eneimines can be employed, a typical example of which (1) A Acylated. is polypropyleneimines. Propyleneimine is now commer- (2) A0 Acylated .then oxyalkylated, Cially available and can be polymerized to the polymer (3) AOA Acylated then oxyalkylated and polypropyleneimine can then be reacted in a manner then arylatei similar to those reactions shown above. Thus, the teach- (4) AOH Acylated then oxyalkylated ings contained herein also apply to other polyalkylenethen heat treated imines besides polycthyleneimine and derivatives thereof. (5) AX Salt or quaternary of (1). (6) AOX Salt or quaternary of (2). USE AS A CHELATING AGENT (7) AOAX Salt or quaternary of (3). This phase of the invention relates to the use of the (8) AOHX Salt or quaternary of (4). compounds of our invention as chelating agents and to (9) O Oxyalkylated. the chelates thus formed. (10) 0A Oxyalkylated, then acylated. Chelation is a term applied to designate cyclic struc- (11) OH 0 x y a l k yl a t e d, then heat tures arising from the combination of metallic atoms with treated. organic or inorganic molecules or ions. Chelates are very (12) K Alkylated. important industrially because one of the unusual features (13) KX Salt or quaternary of (12). of the chelate ring compounds is their unusual stability (14) KA Alkylated, then acylated. in which respect they resemble the aromatic rings of (15) AK Acylated, then alkylated. organic chemistry. Because of the great afiinity of chelat- (16) AKX 1..." Salt or quaternary of (15). ing compounds for metals and because of the great sta- 33 bility of the chelates they form, they are very important industrially.

The compositions of this invention are excellent chelating agents. They are particularly suitable for forming chelates of great stability with a wide variety of metals.

Chelating metals comprise magnesium, aluminum, arsenic, antimony, chromium, iron, cobalt, nickel, palladium, and platinum. Particularly preferred of such metals as chelate constituents are iron, nickel, copper and cobalt.

The chelates formed from the compositions of our invention are useful as bactericidal and fungicidal agents, particularly in the case of the copper chelates. In addition the chelates can be employed to stabilize hydrocarbon oils against the deleterious effects of oxidation.

In general, these chelates are prepared by adding a sufiicient amount of a metal salt to combine with a compound to this invention. They are prepared by the general method described in detail by Hunter and Marriott in the Journal of the Chemical Society (London) 1937, 2000, which relates to the formation of chelates from metal ions and salicylidene imines.

The following examples are illustrative of the preparation of chelates.

Example 1-A7 An aqueous 0.1 mole solution of the chelating agent of Example 1-A is added to an aqueous solution of 0.02 mole cupric acetate. The solution becomes darker in blue color immediately with the formation of the copper chelate. Inability of the solution to plate out copper on a clean and polished iron strip indicates that the copper is effectively removed from the solution by the formation of a chelate.

Example 1-0 An aqueous solution of 0.1 mole of the chelating agent of Example 1-O is added to an aqueous solution containing 0.025 mole ferrous sulfate. Lack of the usual formation of a red sediment in the water subsequently due to oxidation and precipitation of iron as hydrated oxide shows the iron had been chelated while in the ferrous form .by the reagent 1-0 and thus effectively removed from further reactions.

Example 1A O An aqueous solution of 0.1 mole of the chelating agent 1-A O is treated with an aqueous solution containing 0.01 mole nickelous acetate. The solution turns to a darker green indicating that a chelate type of material had been formed.

To avoid repetitive detail, chelates are formed from the above copper, iron and nickel salts and the compounds shown in the following table.

CHELATING AGENTS 34 CHELATING AGENTS Polypropyleneimine, molecular weight 500 Do 1,000 Do 5,000 Do 10,000 Do 20,000 Do 40,000

15- 17H O H BREAKING AND PREVENTING WATER-IN-OIL EMULSIONS This phase of the invention relates to the use of the products of the present invention in preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. Their use provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

They also provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil, (i.e., desalting).

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. Similar-ly, such demulsifier may be mixed with the hydrocarbon component.

These demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydro. carbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., are often employed as diluents. Similarly, the material or materials employed as the demulsifying agents of this process are often admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials are often used alone or in admixture with other suitable well-known classes of demulsifying agents.

These demulsifying agents are useful in a Water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they are used in a form which exhibit relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 0040,000 or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil .and Water is not significant, because said reagents undoubtedly have solubility within such concentrations.

In practicing the process for resolving petroleum emulsions of the Water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, eg the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the well-head and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fluids through the subsequent lines and fittings suffices to produce the desired degree of mixture of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in diluted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the desirable water content of the emulsion separates and settles from the mass.

The following is a typical installation:

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the efiluent liquids leave the well. This reservoir or container, which may vary from gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amouts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the settling tank to the bottom, so that such incoming fluids do not disturb stratification which takes place during the course of demulsification. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as free water, the other being an outlet at the top to permit the passage of dehydrated oil to a second tank, being a storage tank, which holds pipeline or dehydrated oil. If desired, the conduit or pipe which serves to carry the fluids from the well to the settling tank may include a section of pipe with baffles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some convenient temperature, for instance, to F., or both heater and mixer.

Demulsification procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,000. As soon as a complete break or satisfactory demulsification is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufficient to produce clean or dehydrated oil. The amount being fed at such stage is usually 1210,000, l:l5,000, 1120,000, of the like. However, with extremely diflicult emulsions higher concentrations of demulsifier can be employed.

In many instances the products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. Selection of the solvent will vary, depending upon the solubility characteristics of the product, and, of course, will be dictated in part by economic consideration, i.e., cost. The products herein described are useful not only in diluted form but also admixed with other chemical demulsifiers.

In recent years pipe line standards for oil have been raised so that an effective demulsifier must not only be able to break oil field emulsions under conventional conditions without sludge, but at the same time it must also yield bright pipeline oil, i.e., pipeline oil that is free from the minute traces of foreign matter, whether suspended water or suspended emulsion droplets due to nonresolvable solids. In addition the water phase should be free of oil so as not to create a disposal problem. Thus it is presently desirable to use a demulsifier that produces absolutely bright, haze-free oil in the top layer, yields little or no interphasal sludge, and has little if any oil in the water phase.

The following examples show results obtained in the resolution of crude petroleum emulsions obtained from various sources.

EXAMPLES These compounds are tested on water-in-oil emulsions from many areas, the emulsions selected on the basis that they are particularly resistant to treatment. For testing procedure see U.S. Patent 2,626,929 to De Groote.

A field trial is run on compound 1A O at the Shell Oil Company, Pasuncula Lease, San Joaquin Valley, Calif. This system is unusually difficult to demulsify due to a large number of gas lift wells producing highly emulsified oil. One part of demulsifier resolves approximately 30,000 parts of emulsion. The eflluent water from the heater is free from oil and solids.

Similarly, demulsification is effected by employing the compounds shown in the following table on emulsions taken from the following leases:

(1) Texaco Oil Company, Hammond Lease, Gato Ridge, Calif. This oil gravity is 9.1 API and requires a temperature of l80 F. to break the emulsion.

(2) Morton-Kohl'bush Oil Company, Composite, Torrance, Calif. This emulsion broke to 25% water.

(3) Christiana Oil Company, Hayes #1, Wilmington, Calif. This oil has a gravity of 142 API. The emulsion breaks to 34% water. This water has a salivity of 2,127 grains per gallon.

(4) Shell Oil Company, Lease 10-4, Dominquez, Calif. The test temperature was 90 F. Chemical is added at a ratio of 1 to 8000. Water content 20%.

(5) Huntington State Oil Company, Reading #1 37 Lease, Huntington Beach, Calif. This emulsion contained 38% water.

Demulsification was also effective in other areas such as in Texas, Oklahoma, 111., the Rocky Mountain States, Wyoming, etc.

The following compositions are exemplary of effective demulsifiers:

WATER-IN-OIL DEMULSIFIERS 2 03 I-OZHKA 18-0 23-O AU WATER-IN-Oll DEMULSIFIERS Polypropyleneimine, molecular weight 500 Do 1,000 Do 5,000 Do 10,000 Do 20,000 Do 40,000

3 1-0 28O KA 32-0 20A O HKA PREVENTION OF EMULSIONS IN OILS DURING TRANSIT Because of their demulsification properties the compounds of this invention are also useful in preventing the formation of emulsions during transit.

Often oil which meets specifications when shipped arrives emulsified at its destination when extraneous water becomes mixed with the oil during transit through pipe lines, storage in tanks during transportation in seagoing tankers and the like.

For example, as is well known in a number of places where petroleum is produced containing a minimum amount of foreign matter and is completely acceptable for refinery purposes prior to shipment, it is notacceptable after a shipment has been made, for instance, thousands of miles by tanker. The reason is that an empty tanker employs sea water for ballast prior to reloading and it is almost impossible to remove all ballast sea water before the next load starts. In some instances a full tanker may use sea water for ballast also. In other instances, due to seepage, etc., contamination takes place. The rolling or rocking effect of the sea voyage seems to give all the agitation required. It is to be noted that the emulsion, generally a water-in-oil type, so produced is characterized by the fact that the dispersed phase is sea water.

Typical examples are shipments of oil from the Near East to Japan, Australia, etc., and various quantities shipped to the west coast of the USA. and, for that matter, to the east coast of the U.S.A.

The presence of water in petroleum distillate fuels often results in emulsion formation especially when such water-containing fuels are subjected to agitation or other conditions promoting emulsification. Unless such emulsion formation is retarded or emulsions that have been formed are resolved so as to permit separation of water from the fuel, the water entering the fuel system de leteriously affects the performance of the system, particularly mechanisms therein of ferrous metals with which the water-containing fuel comes into contact.

As an example, serious difliculties arise in marine operations when salt water, in amounts even as low as 0.01% by weight of a diesel fuel, enters disel engines. The presence of water in the fuel enhances emulsification thereof and some of the emulsion normally passes through filtering media in the same manner as the fuel that has not been emulsified and, as a result, rapid engine failures often occur. Such failures are often due to corrosion of metal surfaces, as is manifested by surface pitting and formation of fatigue cracks on machined parts, to deleterious effects on fuel injectors resulting in broken or completely disintegrated check valve springs, to promotion of seizure of plungers in bushings and general corrosion of metal surfaces that are contacted by the watercontaining fuel. Accordingly, the presence of water in petroleum distillate fuels, and particularly in diesel fuels, is highly undesirable and means are generally employed to separate the water, often in emulsified form, from the fuel. When the water present in the fuel is in emulsified form, one method for treating the emulsion to prevent water from entering the system is to break the emulsion and separate water from the fuel. As manufactured, petroleum distillates suitable for use as fuels are normally water free or contain not more than a trace of water and, hence, such distillates per se present little, if any, difficulty from emulsification unless extraneous water hecomes admixed therewith.

In illustration reference is made to a current Navy Department Specification for diesel fuels which, in listing the chemical and physical requirements for conformance therewith, sets forth that the diesel fuels must not contain more than a trace, as a maximum, of water and sediment. Nevertheless, and in the handling of such fuels through pipelines, storage thereof in tanks, and during transportation such as in seagoing tankers, extraneous water oftentimes becomes admixed with the fuel thereby providing difiiculties inclusive of those aforesaid.

Oil in transit can be effectively inhibited against emulsification by adding a small amount, i.e., suflicient to substantially reduce the tendency of the fuel to emulsify, of the demulsifiers described above.

In practicing this phase of the invention, the contemplated demulsifiers may be added in desired amounts to a fuel oil that has emulsified as a result of water having become admixed therewith or may be added to a fuel 011 to suppress emulsification thereof when such oils are subsequently exposed to conditions promoting emulsification by admixture of water therewith. For such purposes, the demulsifiers of the present invention may be employed per se, in mixtures thereof, or in combination with a suitable vehicle e.g., a petroleum fraction, to form a concentrated solution or dispersion for addition to the fuels to be treated. For example, when it is desired to add the demulsifying agent in the form of a concentrated solution or dispersion, it is preferably that such a solution or dispersion be prepared by employing a vehicle that is compatible with and does not deletriously affect the performance of the petroleum distillate fuel to be treated. Hence, particularly suitable vehicles for preparing concentrated solutions or dispersions of the demulsifying agents include petroleum fractions similar to or identical to the petroleum distillate fuel to be treated in accordance with this invention.

In illustration, such concentrates may comprise a petroleum distillate or other suitable liquid hydrocarbon in admixture with a demulsifier as embodied herein and wherein the demulsifier is present in an amount of about to 75% or higher but preferably to 50% based on the weight of the concentrate. As specific illustrations, such concentrates may comprise a suitable hydrocarbon vehicle, e.g., diesel fuels, kerosenes, semi-aromatic fractions and other mineral oil fractions, in which there is dissolved or dispersed a demulsifier in amounts varying from about 10 to 75% by weight of the concentrate, and, in still more specific illustration, a suitable concentrate comprising about 50% by weight of demulsifier in admixture with a petroleum hydrocarbon.

In practice, the general procedure is either to add the compound of this invention at the refinery or at the loading dock using a proportional pump. The pumping device adds the product so that it is entirely mixed and thus insures that the cargo oil meets all the required specifications on arrival.

The amount of active emulsion preventive added will vary depending upon many factors, for example, the fuel oil, the amount of agitation encountered, the amount of water, etc. In most cases suitable results are obtained employing 10-75 ppm. of demulsifier to oil but preferably 25-50 p.p.m. In certain oils, the lower concentrations are satisfactory whereas with certain more readily emulsifiable oils, the higher concentrations are desirable.

In order further to describe this phase of the invention, several of the test compositions are prepared by dissolving p.p.m. of the following compounds of this invention in a diesel fuel, mixing the thus prepared solution With an equal amount of either distilled water or synthetic sea water, and subjecting the resulting admixtures to stirring at the rate of 1500 revolutions per minute. Blanks are prepared by mixing the diesel fuel with distilled water or synthetic sea Water in equal amounts. The test compositions containing no demulsifier form emulsions which persist for long periods of time after stirring is stopped. Test compositions containing the compounds shown in the following table either do not emulsify or the emulsions are completely resolved within a short time after stirring is stopped.

EMULSION PREVENTIVE FOR OIL DURING TRANSIT 1-A 19-O K S-K, 20-A O C BREAKING OIL-IN-WATER-EMULSIONS This phase of the invention relates to the use of the products of this invention in a process for preventing, resolving or separating emulsions of the oil-in-water class.

Emulsions of the oil-in-water class comprise organic oily materials, which, although immiscible with water or aqueous or non-oily media, are distributed or dispersed as small drops throughout a continuous body of nonoily medium. The proportion of dispersed oily material is in many and possibly most cases a minor one.

Oil-field emulsions containing small proportions of crude petroleum oil relatively stably dispersed in water or brine are representative oil-in-water emulsions. Other oil-in-water emulsions include: steam cylinder emulsions,

in which traces of lubricating oil are found dispersed in condensed steam from steam engines and steam pumps, wax-hexane-water emulsions, encountered in de-waxing operations in oil refining; butadiene tar-'in-Water emulsions, encountered in the manufacture of butadiene from heavy naphtha by cracking in gas generators, and occurring particularly in the wash box waters of such systems; emulsions of flux oil in steam condensate produced in the catalytic dehydrogenation of butylene to produce butadiene; styrene-in-Water emulsions in synthetic rubber plants; synthetic latex-in-Water emulsions, found in plants producing copolymer butadiene-styrene or GRS synthetic rubber; oil-in-water emulsions occurring in the cooling water systems of gasoline absorption plants; pipe press emulsions from steam-actuated presses in clay pipe manufacture; emulsions of petroleum residues-in-diethylene glycol, in the dehydration of natural gas.

In other industries and arts, emulsions of oily materials in water or other non-oily media are encountered, for example, in sewage disposal operations, synthetic resin emulsion paint formulation, milk and mayonnaise processing, marine ballast water disposal, and furniture polish formulation. In cleaning the equipment used in processing such products, diluted oil-in-water emulsions are inadvertently, incidentally, or accidentally produced. The disposal of aqueous wastes is, in general, hampered by the presence of oil-in-water emulsions.

Essential oils comprise non-saponifiable materials like terpenes, lactones, and alcohols. They also contain saponifiable esters or mixtures of saponifiable and non-saponifiable materials. Steam distillation and other production procedures sometimes cause oil-in-Water emulsions to be produced, from which the valuable essential oils are difficultly recoverable.

In all such examples, a non-aqueous or oily material is emulsified in an aqueous or non-oily material with which it is naturally immiscible. The term oil is used herein to cover broadly the water-immiscible materials present as dispersed particles in such systems. The non-oily phase obviously includes diethylene glycol, aqueous solutions, and other non-oily media in addition to water itself.

The foregoing examples illustrate the fact that, within the broad genus of oil-in-water emulsions, there are at least three important sub-genera. In these, the dispersed oily material is respectively non-saponifiable, saponifiable, and a mixture of non-saponifiable and saponifiable materials. Among the most important emulsions of nonsaponifiable material in water are petroleum oil-in-water emulsions. Saponifiable oil-in-water emulsions have dispersed phases comprising, for example, saponifiable oils and fats and fatty acids, saponifiable oily or fatty esters, and the organic components of such esters to the extent such components are immiscible with aqueous media. Emulsions produced from certain blended lubricating compositions containing both mineral and fatty oil ingredients are examples of the third sub-genus.

Oil-in-water emulsions contain widely different proportions of dispersed phase. Where the emulsion is a Waste product resulting from water flushing of manufacturing areas or equipment, the oil content may be only a few parts per million. Resin emulsion paints, as produced, contain a major proportion of dispersed phase. Naturallyoccurring oil-field emulsions of the oil-in-Water class carry crude oil in proportions varying from a few parts per million to about 20%, or higher in certain cases.

This phase of the present invention is concerned with the resolution of those emulsions of the oil-in-water class which contain a minor proportion of dispersed phase, ranging, for example, from 20% or higher down to 50 parts per million or less.

Although the present process relates to emulsions containing for example as much as 20% or more dispersed oily material, many if not most of them contain appreciably less than this proportion of dispersed phase. In 

1. A PROCESS OF BREAKING, PREVENTING, AND SUPPRESSING EMULSIONS WHICH IS CHRACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF AN AGENT SELECTED FROM THE GROUP CONSISTING OF (1) AN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., SAID POLYMER WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES, (2) A SCHIFF BASE REACTION PRODUCT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING SAID POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (3) A SCHIFF BASE REACTION PRODUCT OF AN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATAED POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (4) A SCHIFF BASE REACTION PRODUCT OF AN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (5) AN OXYALKYLATED SCHIFF BASE REACTION PRODUCT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID LINEAR POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS FORMED BY REACTING SAID LINEAR POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES TO FORM SAID SCHIFF BASE REACTION PRODUCT AND THEN REACTING SAID SCHIFF BASE REACTION PRODUCT, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (6) AN ACYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300* C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES, AND (7) AN ALKYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING FROM 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES. 